CN114318057B - High-strength-toughness corrosion-resistant zirconium-cobalt binary alloy and preparation method thereof - Google Patents
High-strength-toughness corrosion-resistant zirconium-cobalt binary alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-strength-toughness corrosion-resistant zirconium-cobalt binary alloy. The alloy is zirconium-cobalt alloy, and the atomic ratios of the two elements are respectively as follows: 98-99.5% of Zr, 0.5-2% of Co and neglecting impurities. The zirconium-cobalt binary alloy has the hardness of 273.6-336.3 HV, the elastic modulus of 43.76-49.22 GPa, the yield strength of 321.1-412.8 MPa and the pitting potential of 0.57-1.42V. The invention solves the defects in the zirconium alloy technology and some problems faced by the zirconium alloy technology, and the researched alloy has good comprehensive performance and relatively low cost.
Description
Technical Field
The invention belongs to the field of zirconium alloy, and particularly relates to a high-strength and high-toughness zirconium-cobalt binary alloy and a preparation method thereof, which can be widely used for experimental research of zirconium-cobalt alloy.
Background
Having higher strength and higher ductility is one of the basic criteria for engineering material selection. In order to provide engineering materials with a high safety factor in the use of various fields, the materials are selected to require a high strength and a high ductility.
Zirconium alloys have numerous advantages, such as: the thermal expansion coefficient and the thermal neutron absorption cross section area are low, and the high-performance high-temperature-resistant material has good machinability, biocompatibility and stable size effect. It also has disadvantages, such as: low strength and easy pitting. According to the existing research, zirconium alloy has been widely applied to many fields of national economy and national defense construction, has application in the biomedical field because of good machinability and biocompatibility, and has small zirconium density, stable size effect and certain application in the aerospace field. Especially has important application in nuclear industry and chemical industry production. However, because of the poor mechanical properties of zirconium alloys, the application range of zirconium alloys is narrow, the application effect is not deep, and the research on high-strength and high-toughness zirconium alloys is still in the development stage at present. However, the high-toughness zirconium alloy has excellent comprehensive performance and great application potential, so how to improve the strength and the corrosion resistance of the zirconium alloy becomes a key link for successfully applying the zirconium alloy in more application ranges.
The nuclear grade zirconium alloy produced in industrial scale includes zirconium tin series and zirconium niobium series. The former alloy is available under the trade names Zr-2 and Zr-4, and the latter is typically represented by Zr-2.5 Nb. In the zirconium-tin alloy, the alloy elements of tin, iron, chromium and nickel can improve the strength, corrosion resistance and heat conductivity of a corrosion-resistant film of the material and reduce the sensitivity of the surface state to corrosion. The nickel in the zirconium-2 alloy has the function of accelerating hydrogen absorption and embrittlement, and in order to overcome the hydrogen embrittlement tendency in the zirconium-2 alloy, a zirconium-4 alloy is developed, which does not contain nickel and has a higher iron content than the zirconium-2 alloy. The zirconium-4 alloy has similar properties to the zirconium-2 alloy except for hydrogen absorption properties. The Nb element has the characteristic of small thermal neutron absorption cross section, not only reduces the absorption amount of the alloy to hydrogen, but also can eliminate the damage of impurity elements such as Ti, C, Al and the like to the corrosion resistance of the zirconium alloy in the smelting and processing processes.
A number of studies have shown that alloys with a simple cubic structure have found widespread use. TiCo and HfCo alloys with simple cubic structures composed of elements of group IVA and VIII can be used as functional or structural materials. In addition, research finds that the alloy has the characteristics of functional materials and engineering structural materials. In recent years, research shows that Co is an alloy element suitable for the low-temperature stability of the B2 phase Zr-based alloy, and in addition, the addition of a small amount of Co also lowers the martensite phase transformation temperature, thereby influencing the shape memory behavior of the B2 phase.
In order to find a research method capable of improving the toughness of the zirconium alloy, the invention researches the research on the mechanical property and the corrosion resistance of the zirconium alloy by adding a small amount of Co element, and provides data and experimental support for the characteristics of a zirconium cobalt functional material and an engineering material.
Disclosure of Invention
The invention aims to find a method for improving the obdurability of zirconium alloy, and provides a novel high-obdurability zirconium-based alloy and a preparation method thereof. Experiments and data show that the toughness of the zirconium alloy can be improved by adding a small amount of Co element, and the zirconium-cobalt binary alloy with high toughness and corrosion resistance is prepared by taking pure zirconium as a base and adding a small amount of Co element under proper technological parameters. The invention solves the defects in the zirconium alloy technology and some problems faced by the zirconium alloy technology, and the researched alloy has good comprehensive performance and relatively low cost.
The technical scheme of the invention is as follows:
the high strength and toughness corrosion-resistant zirconium-cobalt binary alloy is a zirconium-cobalt alloy, and the atomic ratios of two elements are respectively as follows: zr 98-99.5%, Co 0.5-2%, and the impurities are ignored.
The zirconium-cobalt binary alloy has the hardness of 273.6-336.3 HV, the elastic modulus of 43.76-49.22 GPa, the yield strength of 321.1-412.8 MPa and the pitting potential of 0.57-1.42V.
The hardness, the elastic modulus and the yield strength of the zirconium-cobalt binary alloy show a trend of increasing firstly and then decreasing with the increase of Co content, and reach a peak value at 1.5%; the corrosion resistance increases with increasing Co content.
The preparation method of the high-strength-toughness corrosion-resistant zirconium-cobalt-based alloy comprises the following steps of:
(1) respectively putting industrial grade sponge zirconium and pure cobalt into alcohol for ultrasonic cleaning, and then batching according to the atomic ratio by the proportion;
(2) placing the prepared material in a water-cooled copper crucible of a non-consumable vacuum arc melting furnace, and vacuumizing to 5 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon of 0.06 +/-0.005 MPa into the cavity of the electric arc furnace, then smelting, and carrying out turnover smelting for 4-5 times to obtain ingot casting alloy, namely the high-strength-toughness corrosion-resistant zirconium-cobalt binary alloy; wherein the smelting current is 180-240A/S.
The preparation method of the high-toughness corrosion-resistant zirconium-cobalt-based alloy further comprises the following step (4): and after obtaining the ingot casting alloy, carrying out homogenization annealing treatment on the ingot casting by using a tube furnace, heating the ingot casting to 950-1050 ℃ according to the annealing treatment at 3-5 DEG/min, preserving the heat for 4-6 hours, stopping preserving the heat, and slowly cooling to room temperature.
The pure zirconium is industrial grade sponge zirconium with the purity of 99.4 percent, and the purity of the pure cobalt is 99.995 percent.
The invention has the substantive characteristics that:
in the prior art, for improving the performance of a metal material, a small amount of Co element is introduced into pure Zr to prepare the zirconium-cobalt binary alloy with better toughness and corrosion resistance. Experimental data show that compared with pure zirconium, the mechanical properties of the alloy, such as compression resistance and strength and hardness, are improved to a certain extent after a small amount of Co element is added.
The invention has the beneficial effects that:
1. compared with pure zirconium, the prepared zirconium-cobalt binary alloy has obviously higher strength and hardness and excellent corrosion resistance;
2. by adding Co element, the transformation temperature of beta phase to alpha phase is reduced, the alloy is easy to forge and deform, and the microstructure of the alloy is easy to regulate and control. On the other hand, the addition of Co can improve the corrosion resistance of the alloy and further highlight the advantage of Co in corrosion resistance;
3. compared with pure Zr, the compressive strength and toughness of the alloy added with Co element are improved (the yield strength is improved by 142.3MPa to the maximum after the Co element is added, the elastic modulus is improved by 8.07GPa to the maximum, and the ultimate compressive strength is increased by 514.31MPa to the maximum)
4. The zirconium-cobalt alloy has low production cost and simple process and manufacture, and is convenient for research, development and utilization.
Drawings
FIG. 1 is a metallographic optical micrograph of pure Zr obtained in example 1;
FIG. 2 shows Zr obtained in example 299.5Co0.5Metallographic optical micrographs of;
FIG. 3 shows Zr obtained in example 399Co1Metallographic optical micrographs of;
FIG. 4 shows Zr obtained in example 498.5Co1.5Metallographic optical micrographs of;
FIG. 5 shows Zr obtained in example 598Co2Metallographic optical micrographs of;
FIG. 6 is an XRD pattern of alloys prepared in examples 1-5;
FIG. 7 is a graph of the compressive engineering stress strain of alloys prepared in examples 1-5;
FIG. 8 is a graph showing the change in microhardness of alloys obtained in examples 1 to 5.
FIG. 9 is a graph of corrosion resistance soaking test weight loss for alloys made in examples 1-5.
FIG. 10 is a plot of the polarization of the alloys produced in examples 1-5.
Detailed Description
Hereinafter, embodiments of the present invention will be described in further detail to make the technical process, the object of the invention, and the advantages of the invention more apparent.
The invention aims to provide a high-toughness corrosion-resistant zirconium-cobalt-based alloy and a preparation method thereof, aiming at the defects in the prior art and some problems in the prior art. The alloy is zirconium-cobalt alloy, and the atomic ratios of the two elements are respectively as follows: 98-99.5% of Zr and 0.5-2% of Co. The Co content is added from 0.5%, and the sample preparation is gradually increased according to the increasing rule of every 0.5% until the Co content is increased to 2%. Obtaining pure Zr and Zr99.5Co0.5、Zr99Co1、Zr98.5Co1.5、Zr98Co2And (5) five alloy ingots.
The alloy raw materials are smelted according to the proportion to obtain an alloy ingot, then the ingot is annealed by a vacuum tube furnace, the annealing treatment is carried out according to the temperature rise of 4 DEG/min, the temperature is raised to 1000 ℃ and kept for 5 hours, the structure is more uniform, and for the later sample cutting research of the ingot, the error of the experimental result caused by the uneven composition of the same ingot is avoided.
In order to better illustrate the experimental procedures of the present invention, the following will be described and explained in more detail with reference to the examples, which should not be construed as limiting the invention.
Example 1
(1) 30g of industrial grade sponge zirconium with the purity of 99.4 percent is taken to be soaked in a beaker filled with absolute ethyl alcohol for ultrasonic cleaning for 5min, dried after cleaning and placed in a vacuum electric arc furnace for preparation of smelting;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, closing a valve for gas washing, opening a side pumping valve and a vacuum gauge, observing the indication number of the vacuum gauge, closing the side pumping valve when the indication number of the low vacuum gauge is less than 10pa, opening a gate valve, and opening a molecular pump to pump high vacuum to 5 multiplied by 10 when the indication number of the high vacuum gauge is less than 10pa-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.999 percent and the pressure of 0.06MPa into a cavity of an electric arc furnace to be used as protective gas, well positioning an upper electrode and a lower electrode, turning on a power switch, pressing an automatic arc striking switch to move an electric arc onto a material after a fan runs, then lowering the upper electrode, smelting under the current of about 220A/S, turning the ingot after each smelting is finished to ensure that the ingot with uniform components is finally obtained, and repeatedly smelting for 4-5 times to obtain the ingot; during smelting, if the electric arc needs to be moved to other crucibles, the current is adjusted to 49A/S, the upper electrode is lifted to prevent the electric arc from touching the crucible wall in the moving process, then the electric arc is moved to the position above the materials, the upper electrode is lowered, and the large current is adjusted to continue to repeatedly smelt. After smelting is finished, cooling for about 10min before taking materials to prevent materials from being oxidized.
(4) And after the ingot is taken out, annealing the ingot by using a vacuum tube furnace, raising the temperature of the annealing treatment according to 4 DEG/min, raising the temperature to 1000 ℃, and preserving the heat for 5 hours to ensure that the structure of the ingot is more uniform.
(5) The ingot after heat treatment was cut into 3 pieces of size by a wire electric discharge machine (fast wire cut DK7745)
Polishing the cylindrical test sample from coarse to fine by using abrasive paper until no scratch exists, and then performing a compression deformation experiment; cutting 1 cube with the size of 10mm multiplied by 5mm, carefully grinding and polishing with sand paper until no scratch is formed, and then soaking the cube into NaOH solution with the concentration of 5mol/L for weight loss test; 1 piece of a thin piece having a size of 10mm × 10mm × 2mm was cut out, carefully ground with sandpaper and polished to be free from scratches, then, XRD test was performed, the surface of the sample was corroded, observation of the surface morphology structure was performed with a metallographic microscope, as shown in fig. 1, and finally, hardness test was performed.
(6) As a result of the experiment, the hardness of pure Zr was 249HV, and the compression strain of pure Zr was 428.69MPa when it was broken at a strain amount of 5.61% in the experiment for compression deformation.
Example 2
(1) 29.9029g of industrial grade sponge zirconium with the purity of 99.4 percent and 0.0971g of cobalt sheet with the purity of 99.995 percent are respectively soaked in absolute ethyl alcohol, and after ultrasonic cleaning, according to Zr99.5Co0.5The ingredients are mixed according to the design ratio;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, closing a valve for gas washing, opening a side pumping valve and a vacuum gauge, observing the indication number of the vacuum gauge, closing the side pumping valve when the indication number of the low vacuum gauge is less than 10pa, opening a gate valve, and opening a molecular pump to pump high vacuum to 5 multiplied by 10 when the indication number of the high vacuum gauge is less than 10pa-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.999 percent and the pressure of 0.06MPa into a cavity of an electric arc furnace to be used as protective gas, well positioning an upper electrode and a lower electrode, turning on a power switch, pressing an automatic arc striking switch to move an electric arc onto a material after a fan runs, then lowering the upper electrode, smelting under the current of about 220A/S, turning the ingot after each smelting is finished to ensure that the ingot with uniform components is finally obtained, and repeatedly smelting for 4-5 times to obtain the ingot; during smelting, if the electric arc needs to be moved to other crucibles, the current is adjusted to 49A/S, the upper electrode is lifted to prevent the electric arc from touching the crucible wall in the moving process, then the electric arc is moved to the position above the materials, the upper electrode is lowered, and the large current is adjusted to continue to repeatedly smelt. After the smelting is finished, natural cooling is carried out for about 10min before material taking is carried out, so that the material is prevented from being oxidized.
(4) And after the ingot is taken out, annealing the ingot by using a vacuum tube furnace, raising the temperature of the annealing treatment according to 4 DEG/min, raising the temperature to 1000 ℃, and preserving the heat for 5 hours to ensure that the structure of the ingot is more uniform.
(5) The ingot after heat treatment was cut into 3 pieces of size by a wire electric discharge machine (fast wire cut DK7745)
Polishing the cylindrical test sample from coarse to fine by using abrasive paper until no scratch exists, and then performing a compression deformation experiment; cutting 1 cube with the size of 10mm multiplied by 5mm, carefully grinding and polishing with sand paper until no scratch is formed, and then soaking the cube into NaOH solution with the concentration of 5mol/L for weight loss test; 1 piece of a thin piece having a size of 10mm × 10mm × 2mm was cut out, carefully ground with sandpaper and polished to be free from scratches, then, XRD test was performed, the surface of the sample was corroded, observation of the surface morphology structure was performed with a metallographic microscope, as shown in fig. 2, and finally, hardness test was performed.
(6) Zr is measured by compression test on a test machine with the model Instron 598299.5Co0.5Has a hardness of 273.6HV, and Zr was measured in the compression set test99.5Co0.5When the strain amount was 15.69%, fracture occurred, and the compressive stress at this time was 848.5 MPa. The compressive capacity is better compared with pure Zr.
Example 3
(1) 29.8055g of industrial grade sponge zirconium with the purity of 99.4 percent and 0.1945g of cobalt sheet with the purity of 99.995 percent are respectively soaked in absolute ethyl alcohol, and after ultrasonic cleaning, according to Zr99Co1The ingredients are mixed according to the design ratio;
(2) will be prepared intoPlacing the material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, closing a valve for gas washing, opening a side pumping valve and a vacuum gauge, observing the indication number of the vacuum gauge, closing the side pumping valve when the indication number of a low vacuum gauge is less than 10pa, opening a gate valve, opening a molecular pump when the indication number of a high vacuum gauge is also less than 10pa, and pumping high vacuum to 5 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.999 percent and the pressure of 0.06MPa into a cavity of an electric arc furnace to be used as protective gas, well positioning an upper electrode and a lower electrode, turning on a power switch, pressing an automatic arc striking switch to move an electric arc onto a material after a fan runs, then lowering the upper electrode, smelting under the current of about 220A/S, turning the ingot after each smelting is finished to ensure that the ingot with uniform components is finally obtained, and repeatedly smelting for 4-5 times to obtain the ingot; during smelting, if the electric arc needs to be moved to other crucibles, the current is adjusted to 49A/S, the upper electrode is lifted to prevent the electric arc from touching the crucible wall in the moving process, then the electric arc is moved to the position above the materials, the upper electrode is lowered, and the large current is adjusted to continue to repeatedly smelt. After smelting is finished, cooling for about 10min before material taking is noticed, and oxidation of the material is prevented.
(4) And after the ingot is taken out, annealing the ingot by using a vacuum tube furnace, raising the temperature of the annealing treatment according to 4 DEG/min, raising the temperature to 1000 ℃, and preserving the heat for 5 hours to ensure that the structure of the ingot is more uniform.
(5) The ingot after heat treatment was cut into 3 pieces of size by a wire electric discharge machine (fast wire cut DK7745)
Polishing the cylindrical test sample from coarse to fine by using abrasive paper until no scratch exists, and then performing a compression deformation experiment; cutting 1 cube with the size of 10mm multiplied by 5mm, carefully grinding and polishing with sand paper until no scratch is formed, and then soaking the cube into NaOH solution with the concentration of 5mol/L for weight loss test; cutting 1 thin piece with size of 10mm × 10mm × 2mm, carefully grinding with sand paper, polishing to remove scratches, performing XRD test, etching the surface of the sample, and observing the surface morphology structure with metallographic microscopeInspection was carried out, as shown in FIG. 3, and finally a hardness test was carried out.
(6) Measurement of Zr99Co1Has a hardness of 305.2HV, and Zr was measured in the compression set test99.5Co0.5When the strain amount was 15.42%, fracture occurred, and the compressive stress at this time was 818.28 MPa. The compressive capacity is better compared with pure Zr.
Example 4
(1) 29.7077g of industrial grade sponge zirconium with the purity of 99.4 percent and 0.2923g of cobalt sheet with the purity of 99.995 percent are respectively soaked in absolute ethyl alcohol, and after ultrasonic cleaning, according to Zr98.5Co1.5Proportioning the materials according to the design ratio;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, closing a valve for gas washing, opening a side pumping valve and a vacuum gauge, observing the indication number of the vacuum gauge, closing the side pumping valve when the indication number of the low vacuum gauge is less than 10pa, opening a gate valve, and opening a molecular pump to pump high vacuum to 5 multiplied by 10 when the indication number of the high vacuum gauge is less than 10pa-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.999 percent and the pressure of 0.06MPa into a cavity of an electric arc furnace to be used as protective gas, well positioning an upper electrode and a lower electrode, turning on a power switch, pressing an automatic arc striking switch to move an electric arc onto a material after a fan runs, then lowering the upper electrode, smelting under the current of about 220A/S, turning the ingot after each smelting is finished to ensure that the ingot with uniform components is finally obtained, and repeatedly smelting for 4-5 times to obtain the ingot; during smelting, if the electric arc needs to be moved to other crucibles, the current is adjusted to 49A/S, the upper electrode is lifted to prevent the electric arc from touching the crucible wall in the moving process, then the electric arc is moved to the position above the materials, the upper electrode is lowered, and the large current is adjusted to continue to repeatedly smelt. After smelting is finished, cooling for about 10min before material taking is noticed, and oxidation of the material is prevented.
(4) And after the ingot is taken out, annealing the ingot by using a vacuum tube furnace, raising the temperature of the annealing treatment according to 4 DEG/min, raising the temperature to 1000 ℃, and preserving the heat for 5 hours to ensure that the structure of the ingot is more uniform.
(5) Will be provided withThe ingot after heat treatment was cut into 3 pieces of size by a wire electric discharge machine (fast wire DK7745)
Polishing the cylindrical test sample from coarse to fine by using abrasive paper until no scratch exists, and then performing a compression deformation experiment; cutting 1 cube with the size of 10mm multiplied by 5mm, carefully grinding and polishing with sand paper until no scratch is formed, and then soaking the cube into NaOH solution with the concentration of 5mol/L for weight loss test; 1 piece of a thin piece having a size of 10mm × 10mm × 2mm was cut out, carefully ground with sandpaper and polished to be free from scratches, then, XRD test was performed, the surface of the sample was corroded, observation of the surface morphology structure was performed with a metallographic microscope, as shown in fig. 4, and finally, hardness test was performed.
(6) Measurement of Zr98.5Co1.5Has a hardness of 336.3HV, and Zr was measured in the compression set test98.5Co1.5Fracture occurred at a deformation of 17.31%, and the compressive stress at this time was 886.8 MPa. The compressive capacity is better compared with pure Zr.
Example 5
(1) 29.6096g of industrial grade sponge zirconium with the purity of 99.4 percent and 0.3904g of cobalt sheet with the purity of 99.995 percent are respectively soaked in absolute ethyl alcohol, and after ultrasonic cleaning, according to Zr98Co2The ingredients are mixed according to the design ratio;
(2) placing the prepared material in a water-cooled copper crucible of a WK-II type non-consumable vacuum arc melting furnace, closing a valve for gas washing, opening a side pumping valve and a vacuum gauge, observing the indication number of the vacuum gauge, closing the side pumping valve when the indication number of the low vacuum gauge is less than 10pa, opening a gate valve, and opening a molecular pump to pump high vacuum to 5 multiplied by 10 when the indication number of the high vacuum gauge is less than 10pa-3Pa；
(3) Before arc striking smelting, filling high-purity argon with the purity of 99.999 percent and the pressure of 0.06MPa into a cavity of an electric arc furnace to be used as protective gas, well positioning an upper electrode and a lower electrode, turning on a power switch, pressing an automatic arc striking switch to move an electric arc onto a material after a fan runs, then lowering the upper electrode, smelting under the current of about 220A/S, turning the ingot after each smelting is finished to ensure that the ingot with uniform components is finally obtained, and repeatedly smelting for 4-5 times to obtain the ingot; during smelting, if the electric arc needs to be moved to other crucibles, the current is adjusted to 49A/S, the upper electrode is lifted to prevent the electric arc from touching the crucible wall in the moving process, then the electric arc is moved to the position above the materials, the upper electrode is lowered, and the large current is adjusted to continue to repeatedly smelt. After smelting is finished, cooling for about 10min before material taking is noticed, and oxidation of the material is prevented.
(4) And after the ingot is taken out, annealing the ingot by using a vacuum tube furnace, raising the temperature of the annealing treatment according to 4 DEG/min, raising the temperature to 1000 ℃, and preserving the heat for 5 hours to ensure that the structure of the ingot is more uniform.
(5) The ingot after heat treatment was cut into 3 pieces of size by a wire electric discharge machine (fast wire cut DK7745)
Polishing the cylindrical test sample from coarse to fine by using abrasive paper until no scratch exists, and then performing a compression deformation experiment; cutting 1 cube with the size of 10mm multiplied by 5mm, carefully grinding and polishing with sand paper until no scratch is formed, and then soaking the cube into NaOH solution with the concentration of 5mol/L for weight loss test; 1 piece of a thin piece having a size of 10mm × 10mm × 2mm was cut out, carefully ground with sandpaper and polished to be free from scratches, then, XRD test was performed, the surface of the sample was corroded, observation of the surface morphology structure was performed with a metallographic microscope, as shown in fig. 5, and finally, hardness test was performed.
(6) Measurement of Zr98Co2Has a hardness of 320.3HV, and Zr was measured in the compression deformation test98Co2When the strain amount was 21.2%, fracture occurred, and the compressive stress at this time was 943 MPa. The compressive capacity is better compared with pure Zr.
Table 1 shows the measured results of the mechanical properties of all the embodiments of the present invention, and the results show that: when the Co element is added, the strength and hardness of the alloy show more excellent obdurability compared with pure zirconium. Therefore, according to the experimental results in the table and by combining the metallographic phase diagram, the hardness test diagram, the compressive stress strain diagram and the weight loss test diagram of each embodiment, it can be seen that the obdurability (shown in fig. 7 and 8) and the corrosion resistance (shown in fig. 9 and 10) of the novel high obdurability corrosion-resistant zirconium cobalt binary alloy provided by the invention are significantly improved compared with pure zirconium.
Table 1: results of mechanical Properties measurements of examples 1 to 5 of the present invention
The examples show that the hardness, the elastic modulus and the yield strength of the zirconium-cobalt binary alloy obtained by the invention show a trend of increasing and then decreasing along with the increase of the Co content, when the Co content is increased from 1.5% to 2%, the hardness is reduced from 336.3Hv to 320.3Hv, the elastic modulus is reduced from 49.22GPa to 44.19GPa, the yield strength is reduced from 412.8MPa to 385.5MPa, and the mechanical property of the alloy is best when the Co content is 1.5%.
The invention is illustrated by way of example and not by way of limitation, and reference is made to the description of the invention herein to the other variations of the disclosed embodiments which are readily guessed by the researcher in the field of zirconium alloys and cobalt alloys and which are intended to be within the scope of the invention as defined in the claims.
The invention is not the best known technology.
Claims (7)
1. The high strength and toughness corrosion-resistant zirconium-cobalt binary alloy is characterized in that the alloy is a zirconium-cobalt alloy, and the atomic ratios of two elements are respectively as follows: 98-99.5% of Zr and 0.5-2% of Co.
2. The high-toughness corrosion-resistant zirconium-cobalt binary alloy as claimed in claim 1, wherein the hardness of the zirconium-cobalt binary alloy is 273.6-336.3 HV, the elastic modulus is 43.76-49.22 GPa, the yield strength is 321.1-412.8 MPa, and the pitting potential is 0.57-1.42V.
3. The high strength and toughness corrosion-resistant zirconium-cobalt binary alloy as claimed in claim 1, wherein the hardness, elastic modulus and yield strength of the zirconium-cobalt binary alloy show a trend of rising first and then falling with the increase of Co content, and reach a peak value at 1.5%; the corrosion resistance increases with increasing Co content.
4. The preparation method of the high-toughness corrosion-resistant zirconium-cobalt binary alloy as claimed in claim 1, characterized by comprising the following steps:
(1) respectively putting industrial-grade sponge zirconium and pure cobalt into alcohol for ultrasonic cleaning, and then mixing according to the atomic ratio of 98-99.5% of Zr and 0.5-2% of Co;
(2) placing the prepared material in a water-cooled copper crucible of a non-consumable vacuum arc melting furnace, and vacuumizing to 5 multiplied by 10-3Pa；
(3) Before arc striking smelting, filling high-purity argon of 0.06 +/-0.005 MPa into the cavity of the electric arc furnace, then smelting, and carrying out turnover smelting for 4-5 times to obtain ingot casting alloy, namely the high-strength-toughness corrosion-resistant zirconium-cobalt binary alloy; wherein the smelting current is 180-240A/S.
5. The preparation method of the high strength and toughness corrosion-resistant zirconium-cobalt binary alloy as claimed in claim 4, wherein the preparation method of the high strength and toughness corrosion-resistant zirconium-cobalt binary alloy further comprises the step (4): and after obtaining the ingot casting alloy, carrying out homogenization annealing treatment on the ingot casting by using a tube furnace, heating the annealing treatment according to the speed of 3-5 ℃/min to 950-1050 ℃, preserving the heat for 4-6 hours, stopping preserving the heat and slowly cooling to the room temperature.
6. The method for preparing high toughness corrosion resistant zirconium cobalt binary alloy according to claim 4, wherein the purity of industrial grade sponge zirconium is 99.4%, and the purity of pure cobalt is 99.995%.
7. The method for preparing high-toughness corrosion-resistant zirconium-cobalt-based alloy according to claim 4, wherein the purity of the high-purity argon gas is 99.999%.
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